Optical recording elements containing mixture of metallized azo ether and cyanine dyes

ABSTRACT

An optical recording element having a transparent substrate and on the surface of said substrate, a recording layer, a light reflecting layer is disclosed. The recording layer comprises (i) a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group and said phenyl nucleus is free of strong electron withdrawing groups and (ii) a cyanine dye. The recording layer also has, when unrecorded a refractive index, at a selected wavelength from 400 to 660 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is cross referenced to the following titled application filed by the inventors of the present application on the same day as the present case:

U.S. Ser. No. 09/027,078, filed Feb. 20, 1998, entitled OPTICAL RECORDING ELEMENTS COMPRISING NOVEL METALLIZED AZO ETHER DYES.

FIELD OF THE INVENTION

The present invention relates to optical recording elements generally and DVD-R optical recording elements in particular.

BACKGROUND OF THE INVENTION

Optical recording elements for recording and storing digital information are known. One of the currently popular optical recording element is the compact disc or CD. CDs and recordable CDs (CD-Rs) have transformed the personal entertainment, personal computer and data storage industries. CDs and CD-Rs have made it possible to store enormous amounts of pictures, music or data on inexpensive, reliable, mass produced media.

Digital Versatile Disc (DVD) and recordable DVD (DVD-R) optical recording elements are being developed. For reasons stated below these elements have significantly greater storage capacity than CDs.

In CDs and DVDs digital information is stored as low reflective marks on an otherwise reflective background. In this format the optical information is in the form of read only memory or ROM. Optical information is not recorded in real time, but is produced by press molding. In a typical process a substrate is stamped with a master containing the digital information in an embossed form. The stamped substrate, bearing deformations caused by the embossed master, is coated with a reflective layer and then with a protective layer. In the stamped substrate areas having the deformations the reflectivity is lower than in undeformed areas.

DVD elements have significantly more stringent requirements than CDs. The recording wavelength is 635 nm instead of 780 nm; playback wavelengths are 635 nm and 650 nm instead of 780 nm; numerical aperture of the read head is 0.6 instead of 0.5; the track pitch is 0.8 μm instead of 1.6 μm and the minimum mark length is 0.44 μm instead of 0.83 μm. These changes increase the data storage capacity significantly. In DVD the thickness of the stamped substrate is only 0.6 mm instead of 1.2 mm. However a total substrate thickness of 1.2 mm is required to make DVD elements physically stiffer and the same dimension as the popular CDs. This makes them useful in the current population of DVD modified CD players. Generally this is satisfied by forming a laminate structure that includes a substrate on opposite sides of other DVD required layers. Each substrate may be stamped with stored information or only one is so stamped.

It is sometimes desirable to produce an optical recording element that can be recorded in real time. CD-R elements having this capability are known. Such elements have dye containing optical recording layers coated onto a grooved substrate. The recording layer is coated with a reflectivity layer and then a protective layer. Exposure of the element to a laser recording beam operating in the region of 780 nm forming a relatively low reflective mark.

U.S. Pat. No. 5,500,325 to Chapman et al. discloses dye mixtures for optical recording layers. The mixtures comprise metallized azo ether dyes and a second dye. U.S. Pat. No. 5,426,015 discloses optical recording layers comprising metallized azo dianions with two cationic dye counterions.

DVD-R elements are constructed and used similarly to CD-R elements. However in DVD-R elements the shorter recording and playback wavelengths necessitate the development of new and different dye based optical recording layers.

SUMMARY OF THE INVENTION

The present invention provides an optical recording element having a transparent substrate and on the surface of said substrate, a recording layer, a light reflecting layer; wherein the recording layer (a) comprises (i) a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group and said phenyl nucleus is free of strong electron withdrawing groups (such as nitro and alkylsulfonyl) and (ii) a cyanine dye and (b) has, when unrecorded a refractive index, at a selected wavelength from 400 to 660 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.

The elements exhibit good recording sensitivity and excellent light and dark stability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 presents a DVD optical recording element having a single optical recording layer.

FIG. 2 presents a DVD optical recording element having two optical recording layers.

DETAILED DESCRIPTION OF THE INVENTION

Novel metallized azo ether dyes used in the recording layers include those having the formula (I):

wherein;

R₁ represents hydrogen or an alkyl of from 1 to 6 carbons;

R₂ represents hydrogen, an alkyl of from 1 to 6 carbons or alkoxy with 1 to 10 carbons or halogen;

R₃ is free of strong electron withdrawing groups and represents hydrogen, an alkyl of from 1 to 10 carbons or alkoxy with 1 to 10 carbons or halogen;

R₄ represent an alkyl of from 1 to 10 carbons, a substituted or unsubstituted benzyl; an aryl of from 6 to about 10 carbons or a hetaryl of from 5 to about 10 carbons;

Preparation of a nickel complex of 2-amino-3-hydroxy-6-(2-{2-ethoxyethoxy}phenylazo)pyridine illustrates the general procedure for preparing metallized azo ether dyes:

2-({2-Ethoxyethoxy})aniline (2.1 g) was dissolved in a mixture of water (14 mL) and concentrated HCI (4 mL) and the solution cooled in ice. A solution of sodium nitrite (0.72 g) in water (2 mL) was added slowly and the mixture stirred for 1 hour. The diazonium solution was added to a cooled solution of 2-amino-3-hydroxypyridine (1.1 g) and sodium acetate (15 g) in methanol (1000 mL). After 2 hours the reaction mixture was diluted with water and the product filtered off and washed with water. The dried dye was recrystallized from ethyl acetate. The yield was 2.3 g. of material having an nmr spectrum in agreement with the desired product. Conversion to the metallized dye was carried out by refluxing the above dye (2.0 g) with nickel acetate (0.82 g) in methanol (30 mL) for 4 hours. The solution was cooled and the product filtered off. The yield was 2.1 λ max 562 nm ε=8.51×10 ⁴.

Representative compounds within formula I are shown in Table 1.

TABLE 1 Metallized Azo Dyes

Dye No R₁ R₂ R₃ R₄  1 H H H CH₃  2 H H H CH₂CH₃  3 H H H (CH₂)₇CH₃  4 H H H (CH₂)₂OC₂H₅  5 H H m-OCH₃ CH₃  6 H H p-OCH₃ CH₃  7 H H H

 8 H H H (CH₂)₂CH₃  9 H H H (CH₂)₃CH₃ 10 H H H CH₂CH(CH₃)₂ 11 CH₃ H H CH₂CH₃ 12 CH₃ H H (CH₂)₂CH₃ 13 H CH₂CH₃ H CH₂CH₃ 14 CH₂CH(CH₃)₂ H H CH₂CH₃ 15 H H m-CH₂CH(CH₃)₂ CH₂CH₃ 16 H Cl H C₃H₇ 17 H H Cl C₄H₉

Any cyanine dye that can be stabilized by the metallized azo ether dyes and provide mixtures having the refractive indices specified hereinbefore will be useful in the invention. This generally includes indolo-, thia-, and oxacarbocyanines. Representative cyanine dyes that are useful in the invention are presented in Table 2:

TABLE 2 Cyanine Dyes Cyanine Dye Structure A

B

C

D

E

F

G

H

I

J

K

L

M

N

O

P

Q

R

S

T

U

V

W

X

Mixtures of the metallized azo ether dye stabilizer and the cyanine dye(s) are formed to achieve the refractive indices (n and k). These objectives can be achieved by first determining the stability of a selected metallized azoether dye. By considering the refractive indices of the stabilizer and a selected cyanine dye one estimates the mixture ratio that will provide the desired refractive indices. Then the measurement of the refractive indices of a layer of the mixture is made. If the mixture varies from the desired indices, the composition of the mixture is adjusted by changing the ratio of the components. If the desired indices cannot be achieved by adjusting the components of the mixture, a second cyanine dye and/or stabilizer having known refractive indices can be used to achieve the desired result. The mixtures are also tested for light and dark stability. Mixtures having desired properties are presented in Table 3.

TABLE 3 Cyanine Dye And Metallized Azo Ether Dye Stabilized Mixtures Stabilizer Cyanine Ratio *Index No. Dye Stabilizer/Dye n-k/at 650 nm 2 D 1/1 2.22-0.065 i 3 D 1/1 2.19-0.088 i 4 D 1/1 2.12-0.028 i 5 D 1/1 2.27-0.144 i 6 D 1/1 2.11-0.018 i

Optical Recording Elements

Broadly optical elements provided by the invention comprise a light transmitting, typically pregrooved substrate, a dye recording layer overlaying the substrate, a light reflective layer overlaying the light absorptive layer and a protective layer overlaying the light reflective layer. The recording process will produce marks of lower reflectivity than the unmarked areas of the disk when written and read with a diode laser emitting between 400 and 660 nm. The substituents on the dye molecules are selected such that the real part of the complex refractive index (n) of the unwritten recording layer measured with a light source having a selected wavelength from 400 to 660 nm is greater than 1.8 and the imaginary part (k) is less than 0.2.

Several different layer configuration embodiments are possible for DVD optical recording elements. Two embodiments are presented in FIGS. 1 and 2.

In the FIG. 1 embodiment the DVD element comprises the following layer arrangement:

(a) a transparent grooved substrate (1) having a groove width of from 100 to 800 nm; a groove depth of 30 to 270 nm; and a groove pitch of 0.5 to 1.8 μm, usually 0.8 μm or below.

(b) an optical recording layer (2) comprising a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group. The unrecorded recording layer has a refractive index, at a selected wavelength from 645 to 655 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.

(c) a light reflecting layer (3).

(d) a protective layer (4).

(e) an adhesive layer (5).

(f) a protective layer (6).

(g) a reflective layer (7).

(h) a substrate (8).

In the embodiment presented in FIG. 1 one or more of layers (d), (f) and (g) may be omitted.

In the FIG. 2 embodiment the DVD element comprises the following layer arrangement:

(a) a transparent grooved substrate (1) having a groove width of from 100 to 800 nm; a groove depth of 30 to 270 nm; and a groove pitch of 0.5 to 1.8 μm, usually 0.8 μm or below.

(b) an optical recording layer (2) comprising a metallized azoether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has a azo ether substituent ortho to the azo group the recording layer. The unrecorded recording layer has a refractive index, at a selected wavelength from 645 to 655 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.

(c) a light reflecting layer (3).

(d) a protective layer (4).

(e) an adhesive layer (5).

(f) a protective layer (6).

(g) a reflective layer (7).

(h) an optical recording layer (2) comprising a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group. The unrecorded recording layer has a refractive index, at a selected wavelength from 645 to 655 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.

(i) a transparent grooved substrate (8) having a groove width of from 100 to 800 nm; a groove depth of 30 to 270 nm; and a groove pitch of 0.5 to 1.8 μm, usually 0.8 μm or below.

In some FIG. 2 embodiments one or both of the protective layers (d) and (f) may be omitted.

The substrate may be any transparent material that satisfies the mechanical and optical requirements. For DVD-R elements substrates the required groove specifications are mentioned in the description of FIGS. 1 and 2 above. The preferred material is polycarbonate, other materials are glass, polymethylmethacrylate and other suitable polymeric materials.

The preparation of the optical recording elements of the invention is achieved by spin coating of the dye mixture, with or without addenda, from a suitable solvent onto a transparent substrate. For coating, the dye mixture, with or without addenda, is dissolved in a suitable solvent such that the dye is 20 or fewer parts by weight to 100 parts of solvent by volume. The dye recording layer of the element is then overcoated with a metal reflective layer under reduced pressure by resistive heating or a sputter method and finally overcastted with a protective resin.

Coating solvents for the dye recording layer are selected to minimize their effect on the substrate. Useful solvents include alcohols, hydrocarbon halides, cellosolves, ketones. Examples of solvents are 2,2,3,3-tetrafluoropropanol, tetrachloroethane, dichloromethane, methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, 4-hydroxy-4-methyl-2-pentanone. Preferred solvents are alcohols since they have the least effect on the preferred polycarbonate substrates. Mixtures containing these solvents can also be used.

Useful addenda for the recording layer include stabilizers, surfactants, binders and diluents.

The reflective layer can be any of the metals conventionally used for optical recording materials. Useful metals can be vacuum evaporated or sputtered and include gold, silver, aluminum, copper and alloys thereof.

The protective layer over the reflective layer is similarly conventional for this art. Useful materials include UV curable acrylates.

An intermediate layer, to protect the metal layer from oxidation, can also be present.

In DVD elements the adhesives can be applied using screen printing, hot roller and spin coating methods. The adhesives to form the laminates include UV curable adhesives, hot melt adhesives, UV initiated cationic polymeric adhesives and acrylates.

The refractive index values for unrecorded recording layers were determined by coating a layer of the dye to on a silicon wafer. The refractive index values (n and k) were measured by Variable Angle Spectroscopic Ellipsometer (VASE) manufactured by J. A. Woollan Company.

The following examples demonstrate the recording sensitivity and light and dark stability of the optical recording layers provided by this invention.

For each of the dyes studied a complete DVD recording element according to FIG. 1 was prepared as presented in the examples.

EXAMPLE 1

In this example a DVD type optical recording element according to FIG. 1 was prepared and tested. A first assembly was prepared comprising, in the following order, substrate, recording layer, reflective layer and protective layer. The second assembly comprised, in the following order, a substrate, a reflecting layer and a protective layer. This first assembly was then laminated with an adhesive to the second assembly, protective layer to protective layer. The metallized azoether dye for the recording layer was selected from Table 1. The cyanine dye was selected from Table 2.

First Assembly

A polycarbonate substrate having a thickness of 0.6 mm, a diameter of 120 mm and a center hole diameter of 15 mm with a spiral groove on its surface with a width of 300 nm, a depth of 140 nm and a pitch of 0.8 mm, was made by injection molding.

To form the optical recording layer 1 parts by weight of cyanine dye D and 1 parts by weight of a metallized azo ether dye 1 was dissolved with ultrasound at room temperature in 1 hour in 100 parts of 2,2,3,3-tetrafluoropropanol by volume. The solution was filtered through a 0.2 μm filter. The solution was spin coated on the surface of the substrate to an overall optical density of 0.57 at 526 nm. The coating was dried at 60° C. for 30 minutes.

A gold reflective layer was deposited by a sputter process between 19.05 mm and 59.29 mm radii on the recording layer to about 40 nm thickness. For the deposition a Uniline 3000 made by First Light Technologies equipped with a Torus 10 DC magnetron source was used. Ionized argon gas was the gold carrier gas at 6000OWS (+/−1000) deposition energy level.

A protective layer(DaiNippon Daicure SD-220) was spin coated over the gold reflective layer to a thickness of 7 to 11 mm. The protective layer was UV cured by the Fusion F300 series cure station with an ‘H+’ bulb in 2.6 seconds.

Second Assembly

This assembly was prepared as in the first assembly using the substrate, reflective and protective layers but without a recording layer.

The completed DVD element was prepared by laminating the first and second assemblies together through their respective protective layers. The laminate was formed by applying Sony SK7000 UV curable adhesive with an Autoroll 560 print head programmed for individual discs. The adhesive was silk-screened on to the protective layer of each assembly through a 305 mesh Kodak DOC (durable overcoat) silk-screen with a 90 durometer squeegee used at a 70 degree angle. Each assembly was UV cured at a rate of 10.668 meters per minute under a Fusion 450 UV lamp 25.4 cm “H” bulb. The two assemblies were mated adhesive to adhesive on a locating spindle and 35.6 N (8 pound force) was applied for 2 minutes. The thus formed DVD element was allowed to remain at rest on the spindle for 5 minutes (which resulted in about 90% cure). To be fully cured before testing, the DVD element was left to stand for 24 hours.

To test the DVD element a test system consisting of an optical head with a 635 nm laser, a 0.6 NA lens, push-pull tracking, and ½ aperture focusing was used. The optics used circularly polarized light to reduce laser feedback effects. Recording and play back were carried out with the same laser at 3.84 m/s rotational speed. The read power was kept at 0.5 mW. Single frequency marks were recorded with a 1.61 μm mark length at 9 mW write power thereby forming marks of lower reflectivity than the unmarked area when examined with a light source emitting at 635 nm light. When the marks were read with the read laser, through a 30 kHz bandpass filter centered at the mark carrier frequency for this recording layer, a CNR (carrier to noise ratio) of 57 dB was obtained.

EXAMPLE 2

For this example the same substrate, solvent, solution concentration, filter, spin coater, drying conditions, gold deposition process, lacquer layer application, lamination and testing procedure was used as in the first example. To form therecording layer a mixture 1 part by weight of cyanine dye D and I part by weight of metallized azo ether dye 2 was dissolved with ultrasound at room temperature in 1 hour in 100 parts by volume of 2,2,3,3-tetrafluoropropanol. Then the solution was filtered through a 0.2μ filter. The solution was coated on the surface of the substrate by spin coating to an overall optical density of 0.55 at 526 nm. It was dried at 60° C. for 30 minutes. When written with 9 mW write power at 635 nm, a 52 dB CNR was obtained on reading.

EXAMPLE 3

For this example the same disk substrate, solvent, solution concentration, filter, spin coater, drying conditions, gold deposition process, lacquer layer application, lamination and testing procedure was used as in the first example. To form the light absorptive layer a mixture of 1 part by weight of cyanine dye D and 1 parts by weight of metallized azo ether dye 4 was dissolved with ultrasound at room temperature in 1 hour in 500 parts of 2,2,3,3-tetrafluoropropanol by volume. Then the solution was filtered through a 0.2μ filter. The solution was coated on the surface of the substrate by spin coating to an overall optical density of 0.60 at 526 nm. It was dried at 60° C. for 30 minutes. When written with 8 mW write power at 635 nm, a 54 dB CNR was obtained on reading.

EXAMPLE 4 Light Stability

The selected dyes were spin coated on 5.08 by 5.08 cm (2 by 2 inch) polycarbonate slides. Optical density measurements were taken 5 mm from the edge of the slides with a Hewlett Packard 8450A Diode Array Spectrophotometer between 300 nm and 800 nm wave lengths. The slide was exposed through the polycarbonate for sixteen days by a method recommended by the Image Stability Technical Center for standard 50 klux Daylight exposure(ANSI IT9.9- 1990 “Stability of Color Photographic Images” Section 5 Paragraph 5.6 Describes Simulated Indoor Indirect Daylight exposure). After sixteen days the optical densities were re-measured. To calculate the percent optical density loss, from the optical density value at λ-max before light exposure the optical density value after light exposure was subtracted. The resulting value was divided by the optical density value before light exposure and multiplied by one hundred. Results are presented in Table 4:

TABLE 4 Stabilizer Metallized Cyanine Ratio of % Optical Density Loss azoether dye dye from Stabilizer After 16 days 50 Klux from Table 1 Table 2 and Dyes light Exposure  D* 100 1 D 1/1 12.9 2 D 1/1 12.4 3 D 1/1 15.9 4 D 1/1 32.8 5 D 1/1 7.8 6 D 1/1 25.4 *As reference Cyanine dye only

Table 4 shows that the light stability of the dye mixture is significantly improved over that of cyanine dyes alone. The azoether metallized dyes have a significant stabilizing effect on the cyanine dyes.

EXAMPLE 5 Dark Stability

The dyes were spin coated on 5.08 by 5.08 cm (2 by 2 inch) polycarbonate slides. Optical density measurements were taken before incubation with a Hewlett Packard 8450A Diode Array Spectrophotometer between 300 nm and 800 nm wave lengths. The slides were incubated for six weeks in a Hotpack Temperature Humidity Chamber (Model 434304) set at 80° C. temperature and 80% relative humidity with the slides placed, dye side up, in Petri dishes with the tops slightly open. Then optical measurements were taken after six weeks of incubation. To determine the percent optical density loss, from the optical density value at λ-max before incubation the optical density value after incubation was subtracted. The resulting number was divided by the optical density value before incubation and multiplied by one hundred to give the percent loss in optical density as a result of incubation. The results are presented in Table 5:

TABLE 5 Stabilizer % Optical (Metallized Cyanine Ratio of Density Loss azoether dye dye from Stabilizer After 6 weeks at from Table 1) Table 2 and Dyes 80° C./80% RH 1 D 1/1 4.1 2 D 1/1 3.2 3 D 1/1 5.9 4 D 1/1 5.5 5 D 1/1 2.7 6 D 1/1 0.1 Table 5 shows that optical recording elements of the invention have excellent dark stability.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

What is claimed is:
 1. An optical recording element having a transparent substrate and on the surface of said substrate, a recording layer, a light reflecting layer; wherein the recording layer (a) comprises a (i) a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group and said phenyl nucleus is free of strong electron withdrawing groups and (ii) a cyanine dye and (b) has, when unrecorded, a refractive index at a selected wavelength from 400 to 660 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.
 2. An optical recording element having the following layer arrangement: (a) a transparent grooved substrate having a groove width of from 100 to 800 nm; a groove depth of 30 to 270 nm; and a groove pitch of 0.5 to 1.8 μm; (b) a recording layer (i) comprising a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group and said phenyl nucleus is free of strong electron withdrawing groups and (ii) a cyanine dye and (iii) having, when unrecorded, a refractive index at a selected wavelength from 400 to 660 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2; (c) a light reflecting layer; (d) an adhesive layer; and (e) a substrate.
 3. The element of claim 2 also comprising a protective layer between layers (c) and (d).
 4. The element of claim 3 also comprising a protective layer between layers (d) and (e).
 5. The element of claim 4 also comprising a reflective layer adjacent to layer (e).
 6. The element of claim 2, having, between layers (d) and (e), the following additional layers in the recited order: a protective layer; a reflective layer; and a recording layer (i) comprising a metallized azo ether dye having an azo group linking a substituted 3-hydroxypyridine nucleus to a phenyl nucleus wherein the phenyl nucleus has an ether substituent ortho to the azo group and said phenyl nucleus is free of strong electron withdrawing groups and (ii) a cyanine dye and (iii) having, when unrecorded, a refractive index at a selected wavelength from 400 to 660 nm, comprising a real part (n) greater than 1.8 and an imaginary part (k) less than 0.2.
 7. The element of claim 2 or 6 wherein the substrate has a thickness of 0.6 mm and a groove pitch of 0.5 to 1.0 μm.
 8. The element of any one of claims 1-7 wherein the metallized azo ether dye in the recording layer conforms to formula (I):

wherein; R₁ represents hydrogen or an alkyl of from 1 to 6 carbons; R₂ represents hydrogen, an alkyl of from 1 to 6 carbons or alkoxy with 1 to 10 carbons or halogen; R₃ is free of strong electron withdrawing groups and represents hydrogen, an alkyl of from 1 to 10 carbons or alkoxy with 1 to 10 carbons or halogen; R₄ represents an alkyl of from 1 to 10 carbons, a substituted or unsubstituted benzyl; an aryl of from 6 to about 10 carbons or a hetaryl of from 5 to about 10 carbons.
 9. The element of claim 8 wherein the metallized dye is selected from Table 1 as follows: Metallized Azoether Dyes

Dye No R₁ R₂ R₃ R₄  1 H H H CH₃  2 H H H CH₂CH₃  3 H H H (CH₂)₇CH₃  4 H H H (CH₂)₂OCH₂CH₃  5 H H m-OCH₃ CH₃  6 H H p-OCH₃ CH₃  7 H H H

 8 H H H (CH₂)₂CH₃  9 H H H (CH₂)₃CH₃ 10 H H H CH₂CH(CH₃)₂ 11 CH₃ H H CH₂CH₃ 12 CH₃ H H (CH₂)₂CH₃ 13 H CH₂CH₃ H CH₂CH₃ 14 CH₂CH(CH₃)₂ H H CH₂CH₃ 15 H H m-CH₂CH(CH₃)₂ CH₂CH₃


10. The element of claim 9 wherein the metallized azo ether dye is selected from dyes 1, 2, 3, 4 and 5 of Table 1 recited in claim
 9. 11. The element of any one of claims 1-7 wherein the cyanine dye is selected from the dyes of Table 2 as follows: TABLE 2 Cyanine Dyes Cyanine Dye Structure A

B

C

D

E

F

G

H

I

J

K

L

M

N

O

P

Q

R

S

T

U

V

W

X 